Nuclear spin relaxation of sodium cations in bacteriophage Pf1 solutions

The nuclear magnetic resonance (NMR) spectra for the I=3/2 23Na cation dissolved into filamentous bacteriophage Pf1 solutions display line splittings and relaxation times consistent with an interaction between the 23Na nuclear quadrupole moment and the electric field gradient produced by the negatively charged Pf1 particles. The 23Na NMR line splittings and relaxation rates corresponding to magnetization recovery and single, double, and triple quantum coherence decays are measured in Pf1 solutions and compared to theoretical values. The deviation of the observed dc spectral density J0 from the equal first harmonic J(omega0) and second harmonic J(2omega0) values as J(omega0)=J(2omega0) not equal to J0 in these solutions suggests that ion migration in the electric field gradient of the Pf1 particles produces an anisotropic relaxation mechanism. Correlation functions and thus spectral densities for this process are calculated from solutions to the Fokker-Planck equation for radial motion in an electric potential and used to estimate measured relaxation rates. Appropriate electric potentials are generated from the solutions to the Poisson-Boltzmann equation for a charged Pf1 particle in aqueous phase, functions that lead to theoretical estimates of NMR line splittings consistent with experimental observations.     

An ultrafast time‐resolved infrared and UV–vis spectroscopic and computational study of the photochemistry of acyl azides

The photochemistry of pivaloyl, benzoyl, 4‐phenylbenzoyl, and 2‐anthroyl azides has been studied using femtosecond (fs) time‐resolved infrared (TRIR) and UV–vis spectroscopy and interpreted with the aid of computational chemistry. Density functional theory calculations revealed a significant difference in the nature of the lowest singlet excited state for these carbonyl azides. The lowest singlet excited states (S₁) of p‐phenylbenzoyl and 2‐anthroyl azides are (π,π*) in nature, while the pivaloyl and benzoyl azides S₁ states involve (n,π*) excitations. Nevertheless, for all acyl azides studied here, a similar, and intense, IR band at about 2100 cm^?1 has been detected in the ultrafast TRIR experiments following 270 nm excitation. These bands were shifted to lower energy by about 100 cm^?1 relative to the N₃ stretching mode for the ground states of these azides. These 2100 cm^?1 vibrational bands were assigned to the S₁ states of acyl azides in agreement with density functional theory calculations. The decay of the acyl azide S₁ states was described by bi‐exponential functions. The fast component was attributed to the decay of the hot S₁ state and the longer component to the decay of the thermally relaxed S₁ state. A strong and broad transient absorption in the 350–650 nm spectral range was observed in the fs UV–vis experiments for p‐phenylbenzoyl and 2‐anthroyl azides. The carrier of this absorption also decayed bi‐exponentially, and the time constants were in excellent agreement with those found in the fs TRIR experiments. The slow component of the S₁ state decay was found to be dependent on the solvent polarity. When the lifetime of the acyl azide S₁ state is substantially longer than the time constant for vibrational cooling of nascent (hot) isocyanate, the correlation between the S₁ decay and isocyanate formation was clear. The 270 nm excitation populates the S_n (n ≥ 2) states of these acyl azides. It was established that a hot nitrene is produced more efficiently from both the S_n and hot S₁ states than from the relaxed S₁ state of these acyl azides. Thus, time‐resolved study provides direct experimental evidence that the S₁ state is the precursor of nitrene only when the S₁ state is pumped directly and when the S₁ state lifetime is longer than the time constant of vibrational cooling of the newborn nitrene. All of these results are consistent with the data obtained recently for 2‐napththoyl azide. Copyright © 2012 John Wiley & Sons, Ltd.     

Mechanistic insights into the hydrolysis of organophosphorus compounds by paraoxonase‐1: exploring the limits of substrate tolerance in a promiscuous enzyme

We designed, synthesized, and screened a library of analogs of the organophosphate pesticide metabolite paraoxon against a recombinant variant of human serum paraoxonase‐1. Alterations of both the aryloxy leaving group and the retained alkyl chains of paraoxon analogs resulted in substantial changes to binding and hydrolysis, as measured directly by spectrophotometric methods or in competition experiments with paraoxon. Increases or decreases in the steric bulk of the retained groups generally reduced the rate of hydrolysis, while modifications of the leaving group modulated both binding and turnover. Studies on the hydrolysis of phosphoryl azide analogs as well as amino‐modified paraoxon analogs, the former being developed as photoaffinity labels, found enhanced tolerance of structural modifications when compared with O‐alkyl‐substituted molecules. Results from computational modeling predict a predominant active site binding mode for these molecules, which is consistent with several proposed catalytic mechanisms in the literature and from which a molecular‐level explanation of the experimental trends is attempted. Overall, the results of this study suggest that while paraoxonase‐1 is a promiscuous enzyme, there are substantial constraints in the active site pocket, which may relate to both the leaving group and the retained portion of paraoxon analogs. Copyright © 2012 John Wiley & Sons, Ltd.     

A Rapidly Responsive Sensor for Wireless Detection of Early and Mature Microbial Biofilms

Biofilm-associated infections, which are able to resist antibiotics, pose a significant challenge in clinical treatments. Such infections have been linked to various medical conditions, including chronic wounds and implant-associated infections, making them a major public-health concern. Early-detection of biofilm formation offers significant advantages in mitigating adverse effects caused by biofilms. In this work, we aim to explore the feasibility of employing a novel wireless sensor for tracking both early-stage and matured-biofilms formed by the medically relevant bacteria Staphylococcus aureus and Pseudomonas aeruginosa. The sensor utilizes electrochemical reduction of an AgCl layer bridging two silver legs made by inkjet-printing, forming a part of near-field-communication tag antenna. The antenna is interfaced with a carbon cloth designed to promote the growth of microorganisms, thereby serving as an electron source for reduction of the resistive AgCl into a highly-conductive Ag bridge. The AgCl−Ag transformation significantly alters the impedance of the antenna, facilitating wireless identification of an endpoint caused by microbial growth. To the best of our knowledge, this study for the first time presents the evidence showcasing that electrons released through the actions of bacteria can be harnessed to convert AgCl to Ag, thus enabling the wireless, battery-less, and chip-less early-detection of biofilm formation.     

Investigation of lectinized liposomes as M-cell targeted carrier-adjuvant for mucosal immunization

In the present investigation hepatitis B surface antigen (HBsAg) encapsulated liposomes were developed and coupled with Ulex europaeus agglutinin 1 (UEA-1) to increase transmucosal uptake by M-cells of the Peyer's patches. The liposomes were characterized for shape, size, polydispersity and encapsulation efficiency. Bovine submaxillary mucin (BSM) was used as a biological model for the in vitro determination of lectin activity and specificity. Dual staining technique was used to investigate targeting of lectinized liposomes to the M-cells. Anti-HBsAg IgG response in serum and anti-HBsAg sIgA level in various mucosal fluids was estimated by using ELISA, following oral immunization with lectinized and non-lectinized liposomes in Balb/c mice. Additionally, interleukin-2 (IL-2) and interferon-γ (IFN-γ) level in the spleen homogenates was determined. The results suggest that lectinized liposomes were successfully developed, exhibited increased activity with BSM as compared to non-lectinized liposomes and α-l-fucose specificity of the lectinized liposomes was also maintained. The lectinized liposomes were predominantly targeted to the M-cells. The serum anti-HBsAg IgG titre obtained after 3 consecutive days oral immunizations with HBsAg encapsulated lectinized liposomes and boosting after third week was comparable with the titre recorded after single intramuscular prime and third week boosting with alum-HBsAg. Moreover, lectinized liposomes induced higher sIgA level in mucosal secretions and cytokines level in the spleen homogenates. The results showed that the developed surface modified liposomes could be a potential module for the development of effective mucosal vaccines.     

Synergic effect of Type II ZnO/BiVO4 magnetic heterostructures for visible light-driven degradation of bisphenol A and methyl violet

Construction of an effective heterojunction for unimpeded flow of photogenerated charges and their prolonged separation is imperative for environmental photocatalysis. Herein, we have designed an efficient magnetic ZnO/BiVO₄ type-II heterostructure, which was employed for proficient degradation of persistent methyl violet dye with an efficiency of 97.6% in 90 min and a hazardous organic pollutant, namely, bisphenol A. UV-DRS and photoluminescence studies demonstrated that the fabricated nanocomposite exhibited effective light absorption and prolonged charge separation, thereby resulting in high photocatalytic efficacy under visible light irradiation. The efficacy of developed magnetic ZnO/BiVO₄ was also compared with pristine BiVO₄ and undoped magnetic ZnO, which indicated that the constructed heterostructure displayed approximately threefold and sixfold activity in contrast with bare BiVO₄ and undoped magnetic ZnO nanoparticles, respectively. Radical trapping studies, ESR analysis along with GC-MS analysis were conducted to elucidate the mechanistic pathway during the photodegradation process. This work provides a rational technical approach and research ideas for photocatalytic degradation of harmful organic pollutants in an environment-friendly manner by employing energy-efficient LEDs. Besides, good recyclability of catalyst makes it a promising candidate for large-scale applications.     

Trap Level Characterization of Synthetic Quartz

Thermoluminescene (TL) of synthetic quartz specimens under different physical conditions is investigated. An analysis for one of the prominent glow peaks has been done using the peak shape method. Further, on the basis of extracted trap level spectroscopic information, the results are explained. It is found that with different physical conditions characteristics of trapping level changes systematically.